CN101260229A - Polylactic acid base polymer composition, molding products thereof and film - Google Patents

Polylactic acid base polymer composition, molding products thereof and film Download PDF

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Publication number
CN101260229A
CN101260229A CNA2008100912539A CN200810091253A CN101260229A CN 101260229 A CN101260229 A CN 101260229A CN A2008100912539 A CNA2008100912539 A CN A2008100912539A CN 200810091253 A CN200810091253 A CN 200810091253A CN 101260229 A CN101260229 A CN 101260229A
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polylactic acid
film
base polymer
acid base
fluidizer
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CN101260229B (en
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松本太成
新沼馆浩
熊泽贞纪
木村将弘
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Toray Industries Inc
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Poly(lactic acid) polymer compositions each contain an appropriate poly(lactic acid) polymer and a suitable plasticizer having a polyether and/or polyester segment in combination. The composition exhibit satisfactory flexibility and show very small amount of the evaporation, migration and extraction (bleedout) of the plasticizer and losing transparency upon heating. The poly(lactic acid) polymer compositions are useful as formed plastics such as films.

Description

Polylactic acid base polymer composition, its molding and film
The application is to be on June 19th, 2003 applying date, and application number is 03814366.6, and denomination of invention is divided an application for the Chinese patent application of " polylactic acid base polymer composition, its molding and film ".
Technical field
The present invention relates to polylactic acid base polymer composition, its molding and film.In more detail, relate to by fluidizer give flexibility, do not produce that fluidizer volatilizees, oozes out, runs off (bleed-out), the bleaching and problem such as muddiness, polylactic acid base polymer composition, its molding and the film of excellent in te pins of durability when using of when heating.
Background technology
Plastic refuse is mainly by burning or burying and handle in the prior art.But, can produce the problem that generates and discharge harmful side product by burning, and the minimizing of burying ground, the illegal discarded problem that causes environmental pollution etc.Along with the degree of social concern of handling problems for plastic refuse improves day by day, in vogue day by day to the research and development by the plastics with biological degradability of decomposition such as enzyme or microorganism of aliphatic polyester etc.Recently, the special biodegradable fatty polyester of research and development energetically is a poly(lactic acid).
Poly(lactic acid) is by will making lactic acid as raw material by the starch that corn or taro etc. obtains, and the polymkeric substance that further obtains by chemosynthesis.Even poly(lactic acid) is in aliphatic polyester, its mechanical and physical performance, thermotolerance and the transparency are also excellent, so it is in vogue day by day in the research and development of purpose at the various molding with film, thin slice, band, fiber, rope, non-woven fabrics, container etc.But, because poly(lactic acid) its flexibility deficiency when directly using, therefore in for example with packaging packing film or stretch wrappers, agricultural purposes, studied by the interpolation fluidizer and softened with multi-usage film etc.
Open the technology that discloses the fluidizer that adopts phthalic ester etc. in flat 4-335060 number the spy, and this fluidizer usually as vinylchlorid with and widespread use.But carry out under the remollescent situation at the common fluidizer that adds phthalic ester etc., after just adding, show flexibility, but molding is in air atmosphere, when particularly in high-temperature atmosphere, placing for some time, because fluidizer volatilizees, oozes out, produce flexibility and significantly reduce, the problem that the transparency descends.In addition, carry out under the remollescent situation at the common fluidizer of interpolation, in water, particularly fluidizer is extracted out under the atmosphere of hot water, and flexibility significantly reduces, and the transparency reduces.
No. the 5180765th, United States Patent (USP), No. the 5076983rd, United States Patent (USP), spy open and disclose the technology that lactic acid, line style lactic acid oligomer or cyclic lactic acid oligopolymer are used as fluidizer in the flat 6-306264 communique.But, containing the poly(lactic acid) of lactic acid, line style lactic acid oligomer or the cyclic lactic acid oligopolymer of a great deal of, thermostability was low when it was shaped, and perhaps was hydrolyzed easily under common working conditions.Therefore, have bigger defective when being made the molding of film etc. by this composition, i.e. strength degradation in the short period of time is as its poor practicability of molding.
In addition, open the technology that discloses a kind of like this composition in the flat 8-199052 communique the spy, promptly being mixed with the polyalkylene ether in the multipolymer of poly(lactic acid) and polyalkylene ether is the composition of the fluidizer of principal constituent.But, although this technology makes the flexibility of composition reach practical rank, to the volatilization of fluidizer, the inhibition deficiency of oozing out, running off.
In addition, open the spy and disclose a kind of comprising in the flat 8-253665 communique with the composition of lactic acid as the segmented copolymer of the polymkeric substance of principal constituent and polyalkylene ether and poly(lactic acid).But this technology is to prevent that with additional charging property is the technology of purpose, effect for poly(lactic acid) composition contained in the segmented copolymer that adds as anti-static agent, except instruction is undertaken differential looses by improving chemical affinity with matrix (matrix), its molecular weight etc. is not specifically instructed.Open the content of flat 8-253665 communique record for the spy, from the flexibility of composition, when making molding additive (fluidizer) volatilization, ooze out, run off, and bleaching when further suppressing heating, muddy viewpoint set out, though appended embodiment experiment in practice, the improvement in performance deficiency.
As mentioned above, attempt in the prior art to give flexibility by in poly(lactic acid), adding fluidizer, give enough flexibilities but can't provide, when using, can suppress fluidizer and volatilize, ooze out, run off as molding, and bleaching when suppressing heating, muddy technology.
In addition, also in film with the formation of the transparency and stable on heating poly(lactic acid) by mainly giving flexibility, it is applicable to the purposes of refuse bag or agricultural film etc., and by giving flexibility and cohesiveness etc., with its be applicable to packaging packaging film etc. the technology of purposes study.
Particularly in the purposes of packaging packaging film, for example special opening the oriented film that forms as the composition of the resin of main body and aqueous additive with lactic acid class aliphatic polyester by comprising is disclosed in 2000-26623 number.But, when the embodiment that opens record in 2000-26623 number according to the spy attempts to carry out the system film of oriented film in practice, be limited to the flexibility, thermotolerance and the transparency that when just making film, have as the certain level of used for packing foods packaging film, but at room temperature use several time-of-weeks or after keeping, aqueous additive volatilizees easily, oozes out, on packaged object, adhere to aqueous additive, the flexibility and the cohesiveness of film are damaged fully, having shortcoming on practicality, is a kind of insufficient technology fully.
In the technology of record so far, also be unrealized have excellent flexibility, the transparency, thermotolerance, cohesiveness and the packaging packaging film that forms by polylactic acid base polymer composition.
Disclosure of an invention
The 1st form of polylactic acid base polymer composition of the present invention is a kind of polylactic acid base polymer composition, it is to comprise the polylactic acid base polymer composition with crystalline polylactic acid base polymer and fluidizer, it is characterized by fluidizer and be that to have one or more molecular weight in 1 molecule be 1200 or its above poly(lactic acid) fragment, and have polyethers and/or the segmental fluidizer of polyester.
The 2nd form of polylactic acid base polymer composition of the present invention is a kind of polylactic acid base polymer composition, it is to comprise the polylactic acid base polymer composition that has crystalline polylactic acid base polymer, do not have crystalline polylactic acid base polymer and fluidizer, it is characterized by fluidizer is to have polyethers and/or polyester fragment, and not have molecular weight be 1200 or its above segmental fluidizer of poly(lactic acid).
The 3rd form of polylactic acid base polymer composition of the present invention is a kind of polylactic acid base polymer composition, its be comprise have crystallinity, the polylactic acid base polymer of 145 ℃ of fusing point less thaies and the polylactic acid base polymer composition of fluidizer, it is characterized by fluidizer is to have polyethers and/or polyester fragment, and not have molecular weight be 1200 or its above segmental fluidizer of poly(lactic acid).
The 4th form of polylactic acid base polymer composition of the present invention is a kind of polylactic acid base polymer composition, it is to comprise not have crystalline polylactic acid base polymer and fluidizer, and do not contain polylactic acid base polymer composition with crystalline polylactic acid base polymer, it is characterized by fluidizer is to have polyethers and/or the segmental fluidizer of polyester.
Polylactic acid base polymer composition of the present invention has enough flexibilities, when using as molding fluidizer seldom volatilize or ooze out, run off, seldom bleach when heating, muddiness.
The optimised form that carries out an invention
The polylactic acid base polymer that uses in the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form and the 4th form be with L-lactic acid and/or D-lactic acid as principal constituent, the composition from lactic acid in the polymkeric substance is 70 weight % or the polylactic acid base polymer more than it.Polylactic acid base polymer preferably uses the equal poly(lactic acid) that comprises L-lactic acid and/or D-lactic acid in fact.
Usually all the poly(lactic acid) optical purity is high more, and fusing point and crystallinity are high more.The influence of used catalyzer when the fusing point of poly(lactic acid), crystallinity are subjected to its molecular weight and polymerization, but usually optical purity is 98% or equal poly(lactic acid) more than it, fusing point is about 170 ℃, crystallinity is also higher.In addition, along with the optical purity step-down, fusing point and crystallinity also reduce, and for example optical purity is 88% equal poly(lactic acid), and its fusing point is about about 145 ℃, and optical purity is 75% equal poly(lactic acid), and its fusing point is about about 120 ℃.When optical purity was lower than 70%, all poly(lactic acid) did not demonstrate clear and definite fusing point, becomes amorphism.
So-called polylactic acid base polymer has crystallinity, refer to this polylactic acid base polymer is heated make its sufficient crystallisingization after, when in suitable temperature range, carrying out DSC (differential scanning calorimetric analysis device) mensuration, can observe crystallization heat of fusion from the poly(lactic acid) composition.
Known in the manufacture method of poly(lactic acid) have lactide method and a direct polymerization method.The lactide method be with L-lactic acid, D-lactic acid, DL-lactic acid (raceme) as raw material, in case after generating lactide, carry out ring-opening polymerization again, divided for 2 stages made as 2 times of bodies of ring-type.The direct polymerization method be in solvent with the direct dehydrating condensation of these raw materials, adopt 1 stage to make.In the present invention, under the situation of using equal poly(lactic acid), can be the poly(lactic acid) that any method is made.Under the situation of direct polymerization method, owing to there is not the problem that is caused by 2 times of bodies of ring-type in fact, therefore the viewpoint from plasticity, system film is preferred.Under the situation of the polymkeric substance that makes by the lactide method, 2 times of bodies of the ring-type that contains in the polymkeric substance are gasification when being shaped, the cast drum is contaminated when becoming the fusion system of causing film, the reason that the smoothness of film surface descends, therefore when being shaped or in the stage before the fusion system film, preferably make the content of contained 2 times of bodies of ring-type in the polymkeric substance at 0.3 weight % or below it.
The weight-average molecular weight of the polylactic acid base polymer that uses among the present invention is at least 50,000 usually, is preferably 80,000-300,000, and more preferably 100,000-200,000.Molecular-weight average was at least 50,000 o'clock, when making molding such as film, and intensity physicals excellence.
In addition, the polylactic acid base polymer that uses among the present invention also can have the copolymerization poly(lactic acid) that ester forms other monomer component of performance for copolymerization except containing L-lactic acid, D-lactic acid.As copolymerizable monomer component, can enumerate oxyacetic acid, the 3-hydroxybutyric acid, 4 hydroxybutyric acid, the 4-hydroxypentanoic acid, the hydroxycarboxylic acid of 6 hydroxycaproic acid etc., ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, polyoxyethylene glycol, glycerine, the intramolecularly of tetramethylolmethane etc. has the compounds and the derivative thereof of a plurality of hydroxyls, succsinic acid, hexanodioic acid, sebacic acid, fumaric acid, terephthalic acid, m-phthalic acid, 2, the 6-naphthalic acid, m-phthalic acid 5-sodium sulfonate, the intramolecularly of 5-4-butyl-phosphonium sulfoisophthalic acid etc. contains the compounds or derivatives thereof of a plurality of carboxyls.The copolymer composition of the polylactic acid base polymer of Shi Yonging in the present invention, preferred composition of selecting to have biological degradability.
Used fluidizer has polyethers and/or polyester fragment in the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form and the 4th form.
Have the segmental compound of polyethers and/or polyester, because it is higher with the affinity of poly(lactic acid), therefore the plasticizing efficiency height by importing polyethers and/or polyester fragment in fluidizer, can give poly(lactic acid) with the flexibility as the object of the invention.
Fluidizer used in the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form and the 4th form preferably has the polyethers fragment, more preferably in polyethers, have the fragment that forms by polyalkylene ether, further preferably have the fragment that forms by polyoxyethylene glycol.
The polyalkylene ether that has polyoxyethylene glycol, polypropylene glycol or polyethylene glycol-propylene glycol interpolymer etc. at fluidizer, particularly have under the segmental situation that forms by polyoxyethylene glycol, the affinity of itself and polylactic acid base polymer is high especially, so plasticizing efficiency excellence of fluidizer, by adding a small amount of fluidizer, just can obtain to have the polylactic acid base polymer composition of needed flexibility.
In addition, have polyalkylene ether at fluidizer, particularly have under the segmental situation that is formed by polyoxyethylene glycol, this segmental molecular-weight average is preferably 1000 or more than it, is more preferably at 2000 or more than it.When molecular-weight average 1000 or its when above, can suppress the volatilization of fluidizer especially.In addition, this molecular-weight average can be as high as 500000 or below it, preferably 20000 or below it usually.Molecular-weight average 50000 or situation below it under, the affinity height of itself and polylactic acid base polymer, plasticizing efficiency is also excellent especially in addition.
The fluidizer that uses among the present invention is under the segmental situation with polyalkylene ether formation, even when heating when being shaped etc., the polyalkylene ether fragment partly exists and is easy to oxidation or pyrolysated tendency, and the oxidation inhibitor of the Hinered phenols of therefore preferred and the following stated, hindered amines etc. or Phosphorus etc. thermal stabilizer carry out and use.
Below the polylactic acid base polymer composition of the present invention's the 1st form is described.
Polylactic acid base polymer composition as the present invention's the 1st form, for comprising polylactic acid base polymer composition with crystalline polylactic acid base polymer and fluidizer, fluidizer is 1200 or the poly(lactic acid) fragment more than it for have one or more molecular weight in 1 molecule, and has polyethers and/or the segmental fluidizer of polyester.
In as the polylactic acid base polymer composition of the present invention's the 1st form, adopt under the situation of equal poly(lactic acid), use optical purity 75% or equal poly(lactic acid) more than it get final product.The polylactic acid base polymer that adopts in the polylactic acid base polymer composition as the present invention's the 1st form does not have under the crystalline situation, can not fully suppress fluidizer volatilization, ooze out and run off.
Polylactic acid base polymer composition as the present invention's the 1st form contains fluidizer, and this fluidizer has polyethers and/or polyester fragment, and further to have one or more molecular weight in 1 molecule be 1200 or the poly(lactic acid) fragment more than it.
The poly(lactic acid) fragment that fluidizer has is preferably 1500 or more than it.The poly(lactic acid) fragment that fluidizer has is 1500 or it is when above, the poly(lactic acid) fragment that fluidizer has is by being embedded in the crystallization that forms as the polylactic acid base polymer of base material, generation is limited in effect in the matrix with the fluidizer molecule, but higher level ground suppress fluidizer volatilization, ooze out and run off.
In addition, the segmental molecular weight of the poly(lactic acid) in the fluidizer be 10000 or its above situation under, the plasticization efficient step-down of fluidizer is difficult to give practical flexibility sometimes.
The fluidizer that uses in the polylactic acid base polymer composition of the 1st form uses the poly(lactic acid) fragment to have crystalline fluidizer, but this fluidizer carry out DSC when measuring gained from the segmental crystallization fusion of poly(lactic acid) heat (Δ H P0) preferably at 3.0J/g or more than it.Δ H P0Be more preferably at 10.0J/g or more than it, further preferred Δ H P0At 20.0J/g or more than it.Δ H P0Measuring method record in an embodiment.
In addition, the fluidizer that in the polylactic acid base polymer composition of the 1st form, uses, the ratio of components that constitutes segmental L-lactic component of its poly(lactic acid) and D-lactic component is 100: 0-95: 5, perhaps be preferably 5: 95-0: 100.Under the situation of adding these fluidizers, the polylactic acid base polymer composition that can obtain to suppress especially the fluidizer volatilization, oozes out and run off.
The polylactic acid base polymer composition of the 1st form of the present invention preferably contains and does not have crystalline polylactic acid base polymer.Do not have crystalline polylactic acid base polymer by containing, except can suppressing fluidizer volatilization, ooze out and running off, bleach when also further the inhibition of higher level ground is heated, muddiness.
The ratio that does not have crystalline polylactic acid base polymer can get final product it according to purposes in the scope of not damaging effect of the present invention.
Polylactic acid base polymer is different with the general polyester of polyethylene terephthalate etc., do each other to mix by 2 kinds or polylactic acid base polymers more than it that composition, fusing point, crystallinity etc. are different and make mixture, when adopting usual method to melt extrude, transesterification reaction also takes place hardly.Therefore, in the polylactic acid base polymer composition of the 1st form, preferably make and contain at least a kind of optical purity in the used polylactic acid base polymer 95% or poly(lactic acid) more than it, and further and with not having crystalline polylactic acid base polymer.By this mode, can be made into the volatilization of abundant inhibition fluidizer, ooze out and run off, and bleach when suppressing heating, the high polylactic acid base polymer composition of thermotolerance of muddiness.
In addition, the polylactic acid base polymer composition of the 1st form of the present invention can be made into molding.The polylactic acid base polymer composition of the present invention's the 1st form is preferably by stretching 1.1 times or make molding more than it at least on the single shaft direction.
By the stretch forming product, can promote the poly(lactic acid) fragment of fluidizer to be embedded in this crystallization simultaneously polylactic acid base polymer oriented crystallineization as matrix.Can further suppress the fluidizer volatilization thus, ooze out and run off.
In addition, owing to, also improved the intensity physicals of molding by oriented crystallineization by the stretch forming product, so can obtain to have simultaneously the molding of flexibility and intensity.
The polylactic acid base polymer composition of the 1st form of the present invention is being made under the situation of molding, and during with the nuclear agent of the promotion crystallization of organic class of the mineral-type of talcum for example etc. or sinapinic acid acid amides etc. etc., the poly(lactic acid) fragment that fluidizer can be had is embedded in the crystallization that forms as the polylactic acid base polymer of matrix, promoted the fluidizer molecule is limited to effect in the matrix, can further suppress the fluidizer volatilization, ooze out and run off by this effect.
In the polylactic acid base polymer composition of the 1st form of the present invention, contain fluidizer, and this fluidizer to have one or more molecular weight in 1 molecule be 1200 or the poly(lactic acid) fragment more than it, and have polyethers and/or polyester fragment.
Have one or more molecular weight in the molecule and are 1200 or its above poly(lactic acid) fragment and have polyethers and/or the segmental fluidizer of polyester for example can obtain by such mode, at first with molecular weight 1200 or polylactic acid low polymer more than it by the usual method polymerization of lactide open loop method or lactic acid condensation polymerization method etc., then with its with have one or its above functional group, form the fluidizer principal constituent have polyethers and/or the segmental compound of polyester reacts acquisition in right amount.In addition, also can be with the compound that forms the fluidizer principal constituent as polymerization starter, by the addition of lactide ring-opening polymerization, perhaps will carry out addition by the dehydrating condensation polymerization of lactic acid as the compound of fluidizer principal constituent as polymerization starter.In addition, can be 1200 or polylactic acid low polymer more than it and form the compound of fluidizer principal constituent and leave the processing that adds hot milling etc. also at molecular weight, the difunctionality compound of dicarboxylic anhydride compounds or diisocyanate compound etc. is made its effect as chain-linking agent, make the two that chemical bonding take place.
Below be 1200 or poly(lactic acid) fragment more than it and have polyethers and/or the specific examples of the segmental fluidizer of polyester describes to having one or more molecular weight in the molecule.
Preparation has the polyoxyethylene glycol (PEG) of hydroxyl end groups on two ends.Under the situation that is common commercially available product, on two ends, has the molecular-weight average (M of the polyoxyethylene glycol (PEG) of hydroxyl end groups PEG) calculate by the hydroxyl value of obtaining by neutralisation etc.Relative two ends have polyoxyethylene glycol (PEG) W of C-terminal BWeight part is being added with lactide W AIn the system of weight part, when on two C-terminals of PEG, fully making lactide carry out the ring opening polyaddition reaction, can obtain substantial PLA (A)-PEG (B)-PLA (A) type segmented copolymer.This reaction can be as required implemented under the catalyzer coexistence of stannous octoate etc.
A segmental number-average molecular weight of poly(lactic acid) of the fluidizer that is formed by this segmented copolymer in fact can be from (1/2) * (W A/ W B) * M PEGObtain.In addition, all part by weight of the relative fluidizer of poly(lactic acid) sheet segment components can be in fact from 100 * W A/ (W A+ W B) % obtains.In addition, remove all part by weight of the relative fluidizer of plasticizing composition of poly(lactic acid) sheet segment components, can be in fact from 100 * W B/ (W A+ W B) % obtains.
Remove the unreacted reactant of the PEG etc. of unreacted PEG or terminal poly(lactic acid) fragment molecular weight less than 1200 at needs, the by product of lactide oligopolymer etc., perhaps under the situation of impurity, applicable following process for purification.
After in the suitable good solvent of chloroform etc., the synthetic fluidizer being dissolved equably, drip the suitable poor solvent of water/methanol mixed solution or ether etc.
Perhaps in big excessive poor solvent, add good solvent solution etc., make its precipitation,, behind the sediment separate out, make solvent evaporates by centrifugation or filtration etc.
Process for purification is not limited to aforesaid method, also can as required aforesaid operations be repeated repeatedly.
In aforesaid method, under the situation of the fluidizer of the segmented copolymer of making PLA (A)-PEG (B)-PLA (A) type, the segmental molecular weight of making of poly(lactic acid) that fluidizer had can be obtained in accordance with the following methods.
By adopting the heavy chloroformic solution of fluidizer, measure the chart that obtains based on 1H-NMR, as (1/2) * (I PLA* 72)/(I PEG* 44/4) * M PEGObtain.In the formula, I PEGBe the signal integration intensity from the hydrogen of the methylene radical of PEG main chain portion, I PLABe signal integration intensity from the hydrogen of the methylene radical of PLA main chain portion.
Lactide reactivity when fluidizer is synthetic is enough high, and makes most lactide all carry out under the condition of open loop addition on the PEG terminal part under the synthetic situation, in most cases is preferably based on the method that 1H-NMR measures the figure of gained.
In the polylactic acid base polymer composition of the present invention's the 1st form, by with have in a part one or molecular weight more than it 1200 or the segmental PLA of poly(lactic acid) (A)-PEG (B)-PLA (A) type segmented copolymer more than it use as fluidizer, can form polylactic acid base polymer composition with enough flexibilities.In addition, when the polylactic acid base polymer composition of the present invention's the 1st form uses as molding, the molding of the film that the formation fluidizer seldom volatilizees, oozes out and runs off etc.
The excellent in te pins of durability when polylactic acid base polymer composition of the present invention's the 1st form uses, and be the composition that fluidizer seldom volatilizees, oozes out and runs off.
The molding of the film that is formed by the polylactic acid base polymer composition of the present invention's the 1st form etc. at normal temperatures or lesser temps when using down, can have been given play to excellent weather resistance.
Below the polylactic acid base polymer composition of the present invention's the 2nd form is described.
Polylactic acid base polymer composition as the present invention's the 2nd form, it is a kind of such polylactic acid base polymer composition, it comprises and has crystalline polylactic acid base polymer, do not have crystalline polylactic acid base polymer and fluidizer, it is characterized by fluidizer is to have polyethers and/or polyester fragment, and not have molecular weight be 1200 or its above segmental fluidizer of poly(lactic acid).
The polylactic acid base polymer composition of the present invention's the 2nd form will have crystalline polylactic acid base polymer and not have crystalline polylactic acid base polymer as necessary composition.Do not have crystalline polylactic acid base polymer not containing, only contain under the situation with crystalline polylactic acid base polymer, the crystallinity height of polylactic acid base polymer composition, the shaping post crystallizationization is spent height, therefore inferior in situation about contact with ebullient water or water vapour, at 100 ℃ or will bleach and muddiness when heating is used below it.
In the polylactic acid base polymer composition of the present invention's the 2nd form, adopting equal poly(lactic acid) as having crystalline polylactic acid base polymer when using, preferably adopt optical purity about 75% or equal poly(lactic acid) more than it.
In the polylactic acid base polymer composition of the present invention's the 2nd form,, preferably adopt the equal poly(lactic acid) of optical purity not enough about 70% adopting equal poly(lactic acid) as not having crystalline polylactic acid base polymer when using.
In addition, in the polylactic acid base polymer composition of the present invention's the 2nd form, comprise fluidizer.The fluidizer that comprises in the polylactic acid base polymer composition of the present invention's the 2nd form has polyethers and/or polyester fragment, and not have molecular weight be 1200 or its above poly(lactic acid) fragment.
Below the polylactic acid base polymer composition of the present invention's the 3rd form is described.
The polylactic acid base polymer composition of the present invention's the 3rd form is a kind of like this polylactic acid base polymer composition, its comprise have crystallinity, the polylactic acid base polymer and the fluidizer of 145 ℃ of fusing point less thaies, it is characterized by fluidizer is to have polyethers and/or polyester fragment, and not have molecular weight be 1200 or its above segmental fluidizer of poly(lactic acid).
The polylactic acid base polymer that the polylactic acid base polymer composition of the present invention's the 3rd form will have 145 ℃ of crystallinity, fusing point less than is as must composition.At this, the fusing point of so-called polylactic acid base polymer refers in-30 ℃ to 220 ℃ scope, and heat-up rate is 20 ℃/minute, adopts DSC to survey the temperature at periodic crystallization fusion peak.The polylactic acid base polymer composition of the present invention's the 3rd form only contains fusing point under the situation of 145 ℃ or polylactic acid base polymer more than it, the fusing point height of polylactic acid base polymer composition, crystallization degree after the shaping becomes too high, therefore inferior in situation about contact with ebullient water or water vapour, at 100 ℃ or will bleach and muddiness when heating is used below it.
Under the situation that adopts equal poly(lactic acid) as polylactic acid base polymer with 145 ℃ of crystallinity, fusing point less than, the equal poly(lactic acid) of preferred optical purity not enough about 88%.
In addition, contained fluidizer has polyethers and/or polyester fragment in the polylactic acid base polymer composition of the present invention's the 3rd form, and not have molecular weight be 1200 or its above poly(lactic acid) fragment.
The polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form, the preferred not enough all 50 weight % of fluidizer of the part by weight of the poly(lactic acid) sheet segment components of its fluidizer.When 50 weight % of the whole fluidizers of deficiency, the plasticizing efficiency of fluidizer is higher, therefore can addition still less obtains the polylactic acid base polymer composition with desirable flexibility.In addition, the part by weight of the poly(lactic acid) sheet segment components of the fluidizer that uses among the present invention also can be made of plasticization component proportions in the fluidizer molecule etc., is generally 5 weight % of whole fluidizers or more than it.
The polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form is preferably determined suitable fluidizer addition according to the characteristic of required flexibility or intensity etc.In addition, the part by weight of the plasticization composition of fluidizer except poly(lactic acid) sheet segment components is preferably the 5 weight %～30 weight % of whole compositions.When the part by weight of the plasticization composition of fluidizer except poly(lactic acid) sheet segment components is the 5 weight %～30 weight % of whole compositions, can obtain the composition of the mechanical properties balance excellence of flexibility and intensity rerum natura etc.
Below the polylactic acid base polymer composition of the present invention's the 4th form is described.
The polylactic acid base polymer composition of the present invention's the 4th form is a kind of such polylactic acid base polymer composition, it comprises and does not have crystalline polylactic acid base polymer and fluidizer, and do not contain polylactic acid base polymer composition with crystalline polylactic acid base polymer, it is characterized by, fluidizer is to have polyethers and/or the segmental fluidizer of polyester.
The polylactic acid base polymer composition of the present invention's the 4th form will not have crystalline polylactic acid base polymer as necessary composition.Adopt equal poly(lactic acid) as not having under the situation of crystalline polylactic acid base polymer, preferably adopting the equal poly(lactic acid) of optical purity not enough about 70%.
In addition, the polylactic acid base polymer composition of the present invention's the 4th form does not contain and has crystalline polylactic acid base polymer.
As the composition except the poly(lactic acid) fragment of used fluidizer in the polylactic acid base polymer composition of the present invention's the 4th form, preferential composition of selecting to have biological degradability.
The polylactic acid base polymer composition of the present invention's the 4th form does not have higher thermotolerance, but particularly useful in the heat seal of the stacked film that for example needs polylactic acid base polymer to form becomes to grade the purposes of under lower temperature plastically deformable.
In the polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form, in the scope of not damaging effect of the present invention, also can comprise as required as known various fluidizers, oxidation inhibitor, ultra-violet stabilizer, anti-coloring agent, matting agent, reodorant, fire retardant, weather resisting agent, static inhibitor, releasing agent, antioxidant, ion-exchanger or as the inorganic particles or the organic compound of tinting pigment etc.
In the polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form, except polylactic acid base polymer and have polyethers and/or the segmental fluidizer of polyester, also contain under the situation of other composition preferential composition of selecting to have biological degradability.
As the present invention's the 1st form, the 2nd form, the known fluidizer that the polylactic acid base polymer composition of the 3rd form and the 4th form can contain, can exemplify out diethyl phthalate, dioctyl phthalate (DOP), the phthalate of dicyclohexyl phthalate etc., hexanodioic acid two-1-butyl ester, di n octyl adipate, n-butyl sebacate, the fatty group dibasic acid of nonane diacid two-2-(ethyl hexyl) ester etc., di(2-ethylhexyl)phosphate phenyl-2-(ethyl hexyl) ester, the phosphoric acid ester of di(2-ethylhexyl)phosphate phenyl octyl group ester etc., tributyl acetylcitrate, acetyl tributyl citrate three-2-(ethyl hexyl) ester, the hydroxyl multivalent carboxylate of tributyl citrate etc., the acetyl methyl ricinoleate, the fatty acid ester of stearic acid amyl group ester etc., Vanay, the polyvalent ester class of triethylene glycol dieaprylate etc., epoxidised soybean oil, the epoxy linseed oil fatty acid butyl ester, the epoxies fluidizer of epoxidation octyl stearate etc., the polyester fluidizer of polypropylene glycol sebate etc., the polyalkylene ethers, the ether-ether class, esters of acrylic acid etc.From the security aspect, preferably adopt the fluidizer of U.S. food board of health (FDA) approval.
Add the method for fluidizer in polylactic acid base polymer, from suppressing the high-polymerization degreeization of polylactic acid base polymer, the viewpoint of remaining lower molecular weight thing etc. is set out, preferably interpolation after the polymer polymerizing reaction is finished, melting mixing fluidizer.As interpolation, the method of melting mixing polylactic acid base polymer and fluidizer, for example can be after polycondensation be just finished, in the polylactic acid base polymer of molten state, add, stir the also method of melting mixing fluidizer, in the thin slice of polylactic acid base polymer, add, after mixing fluidizer, in reactor or forcing machine etc., carry out the method for melting mixing, in forcing machine, heat polylactic acid base polymer etc. as required, it is in a liquid state, add continuously the method for fluidizer and melting mixing, will contain mixing thin slice that the homopolymerization sheet of the master slice of polylactic acid base polymer of high density fluidizer and polylactic acid base polymer mixes and adopt forcing machine etc. to carry out the method etc. of melting mixing.
The oxidation inhibitor that can contain in the polylactic acid base polymer composition as the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form can exemplify out Hinered phenols, hindered amines etc.
The tinting pigment that can contain in the polylactic acid base polymer composition as the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form, can use pigment dyestuff of the mineral dye of carbon black, titanium oxide, zinc oxide, ferric oxide etc. and other cyanine dyes, styrenic, phthalocyanines, anthraquinone class, Perynone (ペ リ ノ Application) class, iso-indole ketone, quinophthalone class, キ ニ Network リ De Application class, thioindigo class etc. etc.
In addition, for improving easy the to be sliding property or the anti-adhesion performance of molding, when in the polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form, adding inorganic particles, can adopt for example silicon-dioxide, colloidal silica, aluminum oxide, alumina sol, kaolin, talcum, mica, lime carbonate etc.Its median size is not particularly limited, and is preferably the 0.01-5 micron, and more preferably the 0.05-3 micron is more preferably the 0.08-2 micron.
In the polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form, in the scope of not damaging effect of the present invention, can also contain polylactic acid base polymer aliphatic polyester in addition.By containing polylactic acid base polymer aliphatic polyester in addition, can reduce melt viscosity or improve biological degradability.
As the aliphatic polyester beyond the polylactic acid base polymer that can in the polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form and the 4th form, contain, can exemplify out polyglycolic acid, poly-(3-butyric ester), poly-(3-butyric ester 3-hydroxyl valerate), polycaprolactone or ethylene glycol, 1, the polyester that the aliphatic diol of 4-butyleneglycol etc. and the aliphatic dicarboxylic acid of succsinic acid, hexanodioic acid etc. form etc.
The polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form can be shaped by fusion, solution state and be processed into film, thin slice, various molding.
The polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form has enough flexibilities, the transparency, intensity physicals, utilizes in can be in than the prior art wideer field.The wrapping material, agricultural film, label that for example can be used as packaging packaging film or stretch wrappers etc., container class, the seedling-growing container of the bottle of the industry data of motor vehicle paint film-protecting sheet, refuse bag, compost bag etc., Industrial materials purposes, beverage or makeup, sanitary cup, plate etc., are planted tub etc. and are utilized with film, base material protection film with film, adhesive tape.
Be configured as under the situation that film uses at polylactic acid base polymer composition the present invention's the 1st form, the 2nd form, the 3rd form, can by blowing process, successively biaxial stretch-formed method, the manufacture method of existing oriented film obtains film in the prior art such as biaxial stretch-formed method simultaneously.
Under the situation that adopts biaxial stretch-formed successively method, biaxial stretch-formed manufactured film of while, can adopt known method that polylactic acid base polymer composition is melt extruded the flakiness shape by the slit-shaped die orifice, by being fitted on the casting drum, make its cooling curing, obtain not tensile film.
In polylactic acid base polymer, add the method for fluidizer, for making its thermal degradation when be restricted to minimum to composition, preferably by using biaxial extruder etc., fused polylactic acid base polymer in the forcing machine heated etc. as required make liquid state, add continuously on metering fluidizer limit, limit, carries out the method for melting mixing.In addition, the parent thin slice of polylactic acid base polymer that can also be by will containing the high density fluidizer and the homopolymerization thin slice of polylactic acid base polymer are mixed and made into the mixing thin slice, this mixing thin slice is provided to the system of extruding of the film-making machine of forcing machine etc. carry out melting mixing.
Under the situation of making film, after will stretching at least in one direction continuously with the non-stretched film that aforesaid method produces, heat-treat as required.For example when 100 ℃ or temperature more than it are heat-treated, can obtain to be suitable for the low film of excellent in dimensional stability, percent thermal shrinkage of various films such as packaging packaging film or agricultural film.In addition, not heat-treating or being lower than when heat-treating under 100 ℃ the temperature, can obtain to be suitable for the film with higher thermal shrinking percentage of shrink packaging with film etc.
When the molding of the film that the polylactic acid base polymer composition of the present invention's the 1st form is made etc. uses, can bring into play excellent weather resistance under normal temperature and lesser temps.
In addition, the polylactic acid base polymer composition of the present invention's the 2nd form, the 3rd form, the 4th form significantly suppresses to bleach in the time of can forming particularly heating use, muddiness, and the composition of excellent in te pins of durability.
The polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form be easy to generate fluidizer volatilization or ooze out, effective especially in the molding fields such as film of losing issue.
With the polylactic acid base polymer composition of the present invention's the 1st form, the 2nd form, the 3rd form as for example, under the situation that the packaging packaging film uses, when just bringing into use, have enough flexibilities, the transparency and intensity physicals in the practicality simultaneously, in use for some time, in fact almost do not have the volatilization of fluidizer yet or ooze out, run off, and heating bleaching when using, muddiness.Therefore, can keep flexibility, the transparency of using when beginning during use for a long time.In addition, containing under the situation with biological degradability plasticizing agent, can obtain after use can be not separate, directly the packaging packaging film of compost with the inclusion of food etc.In addition, owing to have permanent stability, even can obtain after manufacturing through also can not becoming bad for a long time, and the molding of the film of performance performance originally etc.In addition, in the various post-treatment operations of the molding of after shapings such as film system film, implementing, even various xeothermic add in man-hour and the high-temperature atmosphere handle after, also can make by having the stable flexibility and the transparency, even when heating is used, also can not bleach, molding that muddy film etc. forms.
The present invention's the 1st form, the 2nd form, the 3rd form polylactic acid base polymer composition can stretch 1.1 times or more than it at least on the single shaft direction, form the molding of film etc.
The most situation of film that is formed by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form stretches 1.1 times or more than it at least on the single shaft direction, but according to stretching conditions such as draft temperature or stretching (distortion) speed, therefore sometimes the situation that also has uneven pulling is preferably made stretch 2 times or its above, more preferably stretch 2.5 times or its above film.
Under the situation by the present invention's the 1st form lactide acid polymer composition forming film, by on the single shaft direction, stretching 1.1 times or more than it at least, make polylactic acid base polymer oriented crystallineization as parent, promote the poly(lactic acid) fragment of fluidizer to be embedded in this crystallization simultaneously, can further suppress the fluidizer volatilization, ooze out and run off.In addition, owing to also can improve the intensity physicals of film by oriented crystalline, so can make the film that has flexibility and intensity simultaneously.
In addition, when the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form is made biaxial stretch-formed film, preferably be stretched as 4 times or more than it as the area multiplying power of the area ratio of the film before and after stretching, more preferably be stretched as 7 times or more than it.
By the film that the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form is made, preferably its tensile modulus is 100-1500MPa.The tensile modulus of film mainly can be by adjusting fluidizer in the composition addition, kind, film forming condition etc. form desirable value.If tensile modulus is at 1500Mpa or below it; when then using in refuse bag, agricultural multi-usage film, stretch wrappers, label are protected with film, the purposes of bag with film, packaging film etc. with film, adhesive tape with film, base material, ease of use is good.When using as the used for packing foods packaging film, film fully is out of shape with the shape of packed article, therefore obtains enough adaptations easily, thereby preferred.In addition, when tensile modulus when 100Mpa or its are above, the releasing of roll film is good, the engineering trafficability characteristic is good in the system film and the course of processing.
By the film that the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form is made, preferably its thermotolerance is 120-230 ℃.The thermotolerance of film is estimated according to the method for putting down in writing among the embodiment.When thermotolerance when 120 ℃ or its are above, occur in hardly when the system film stretches and be bonded on the warming mill, thermosetting is bonded on the periphery when handling, the problem of system film reblocking etc., engineering stability excellence.And, when the film with gained uses as the used for packing foods label film, even contact with hot water or carry out heat treated with microwave oven, hole or the clinkering situation on packed article takes place hardly also on the film, therefore preferred.
In addition, the film of making by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form, with polylactic acid base polymer as the main composition composition.The upper limit of the fusing point of poly(lactic acid) is generally 230 ℃, and the stable on heating higher limit of film of the present invention also is based on this.
Even the fusing point of poly (l-lactic acid) is 98% or it is when above in its optical purity, near about 170 ℃, form the fusing point that the so-called three-dimensional complex crystallization of crystalline demonstrates 220-230 ℃ of vicinity in pairs but form polylactic acid molecule (for example poly (l-lactic acid) and poly-D-lactic acid) mutually by optical isomer.Particularly in film, give under the stable on heating situation that is higher than 170 ℃ in advance, for the molding of making by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form, also can and be respectively 95% or poly (l-lactic acid) and poly-D-lactic acid more than it with optical purity as polylactic acid base polymer.
In addition, under the situation of the molding of making by the polylactic acid base polymer composition of the 1st form of the present invention in particular for film, as polylactic acid base polymer, use optical purity at least 95% or poly (l-lactic acid) more than it, the poly(lactic acid) fragment that has at fluidizer can adopt from the composition of D-lactic acid for its weight 98% or it is with first-class formation.
In addition, at the molding of making by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form, particularly in film, in order further to promote the generation of three-dimensional complex crystallization, in the preferred polylactic acid base polymer composition that uses from the composition of L-lactic acid with from the composition weight equivalent or the approximate equivalent of D-lactic acid.
The film of being made by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form itself has the excellent transparency, film turbidity value and is preferably 0.2-5%.The film turbidity value refers to by carry out ratio from the practical measurement value and calculates according to the method evaluation of embodiment record, is scaled film thickness and is the value of gained under 10 microns the situation.Particularly in the purposes of the used for packing foods packaging film in the packaging packaging film,, can see inclusion easily if when the turbidity value of film is 0.2-5%, therefore suitable.In addition, would rather need certain disguise, in the higher purposes of the specific absorption of the low or sunlight of perhaps preferred light penetration etc., for example can add tinting pigment etc. as required at refuse bag or agricultural film etc.
Preferred its cohesive force of film of being made by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form is 5-30N/cm 2Cohesive force is estimated according to the method for embodiment record.When cohesive force is 5-30N/cm 2The time, particularly when using as the used for packing foods packaging film, can not take place completely to peel off naturally because cohesive force is not enough, perhaps film sticks together, from the bad phenomenon of the roller property removed change, and have drawing mechanical performance and appropriate in use cohesiveness, can form packaging film easy to use.
Thickness to the film made by the polylactic acid base polymer composition of the 1st form of the present invention, the 2nd form, the 3rd form is not particularly limited, and can suitably determine thickness according to purposes.The thickness of film is generally 5 microns～1mm, especially preferentially selects 5 microns～200 microns.In addition, in packaging packaging film or stretch wrappers, during as the used for packing foods packaging film, preferably in 5 microns～25 microns scope, select.
In addition, the polylactic acid base polymer composition of the 1st form, the 2nd form, the 3rd form is made film shaped after, also can carry out various surface treatments in order to improve printing, lamination adaptability, coating adaptability etc.As the surface-treated method, can enumerate Corona discharge Treatment, Cement Composite Treated by Plasma, flame treating, acid treatment etc., also can adopt any method.Surface treatment be from handling continuously, aspect being provided with from device at existing membrane equipment easily and handle simplicity, most preferably Corona discharge Treatment.
(embodiment)
Followingly the present invention is elaborated, but the invention is not restricted to following embodiment according to embodiment.
In addition, in following embodiment, as the promotion experiment that promotes that fluidizer volatilizees, oozes out, runs off, weight decrement after the mensuration dry heat treatment and the weight decrement after the hot-water cure.Physicals among the embodiment is measured in accordance with the following methods.
(1) modulus in flexure [MPa]
Adopt テ Application シ ロ Application universal testing machine RTC-1310 type (the オ リ エ of Co., Ltd. Application テ StarNetwork) implements pliability test (JIS K 6911).The width that makes test film is 12mm, and thickness is 6mm, and the clamp spacing is 120mm, and trial speed is 3mm/ minute, tests under 30 ℃ atmosphere.
(2) the weight decrement [%] after the dry heat treatment
At first to the weight before under the humidity atmosphere of 23 ℃ temperature, 65%RH, carrying out 1 or the compressing tablet or the biaxially oriented film sample of its above damping, measure it handling.Then, in 90 ℃ hot-air oven, handle after 30 minutes, once more according to handle before the same condition damping, after this measure its weight.The weight decrement is according to calculating with respect to the ratio of changes in weight (weight minimizing) before and after the processing of the weight before handling.
(3) the weight decrement [%] after the hot-water cure
At first to the weight before under the humidity atmosphere of 23 ℃ temperature, 65%RH, carrying out 1 or the compressing tablet or the biaxially oriented film sample of its above damping, measure it handling.Then, in 90 ℃ distilled water, handle after 30 minutes, once more according to handle before the same condition damping, after this measure its weight.The weight decrement is according to calculating with respect to the ratio of changes in weight (weight minimizing) before and after the processing of the weight before handling.
(4) transparency keep temperature [℃]
The length of side in the frame inside dimension is on the aluminium sash of 150mm, paste to pay estimate with compressing tablet or film sample with the Stress that does not produce fold, use a plurality of stationery double fasteners, film is fixed on the framework, place it in the hot air type baking oven that keeps in the storehouse at a certain temperature, take out after 30 minutes and range estimation observation sample state.Design temperature with the hot air type baking oven only changes 5 ℃ at every turn, and revision test is obtained and confirmed that sample does not bleach, muddiness, and transparent unconverted top temperature keeps temperature as the transparency.
(5) heat (Δ H is separated in the crystallization fusion P0) [J/g]
At first fluidizer was handled 3 hours under 90 ℃, 1Torr or the decompression below it, made its thorough drying and crystallization.Then, fusing point at 90 ℃ or fluidizer below it does not carry out drying, crystallization is handled, is directly used in mensuration.Accurately the about 5mg sample of weighing on its predetermined platter of packing into, adopts differential scanning calorimetric analysis device (DSC) RDC220 of セ イ コ one electronic industry (Co., Ltd.) manufacturing, is warming up to 220 ℃ with 20 ℃/minute from-30 ℃ under nitrogen atmosphere.From the heat diagram of gained, read out from the segmental crystallization of the poly(lactic acid) of fluidizer and melt heat (Δ H P0).
(6) tensile modulus [MPa]
To estimate and make width with thin slice is 10mm, and length is the sheet of 150mm, at first carries out 1 day under the humidity atmosphere of 23 ℃ temperature, 65%RH or the damping more than it is handled.Adopt this diaphragm, make that the clamp spacing is 50mm, draw speed is the 300mm/ branch, adopts テ Application シ ロ Application universal testing machine UTC-100 type (the オ リ エ of Co., Ltd. Application テ StarNetwork), under 23 ℃ atmosphere, carries out tension test, measure tensile modulus.Be during mensuration under each level, measure in the longitudinal direction 5 times, on width, measure 5 times, amount to 10 times, obtain the mean value of 10 tests, with it as tensile modulus.
(7) thermotolerance [℃]
The length of side in the frame inside dimension is on the aluminium sash of 150mm, paste a pair evaluation film with the Stress that does not produce fold, use a plurality of stationery double fasteners, film is fixed on the framework, place it in the hot air type baking oven that keeps in the storehouse at a certain temperature, place after 5 minutes, take out and range estimation observation filminess.At every turn the design temperature with the hot air type baking oven only changes 5 ℃, and revision test confirms that the hole does not take place film sample, and perhaps not clinkering of film is in the top temperature of the first-class variation of framework, with it as showing stable on heating temperature.
(8) film turbidity value [%]
As the film sample index of transparency, at first adopt turbidometer HGM-2DP type (manufacturing of ス ガ trier Co., Ltd.) measure thickness after measured the turbidity value of film sample.Each benchmark is measured 5 times during mensuration, and being converted into thickness with the mean value of measuring by 5 times is scaled value under 10 microns the film situation, obtains film turbidity value %.
(9) cohesive force [N/cm 2]
With 2 width is 10mm, and length is that the diaphragm of 100mm is made into 1 group, at first carries out 1 day under the humidity atmosphere of 23 ℃ temperature, 65%RH or the damping more than it is handled.After this, continue in identical atmosphere, 10mm part on the tip lengths direction of single sheet of thin diaphragm and the 10mm part on another sheet diaphragm tip lengths direction respectively the film length direction equate overlapping in opposite directions.Additional 50g/cm on the eclipsed part 2Load, placed 1 minute, make and measure the cohesive force sample.When measuring cohesiveness, adopt テ Application シ ロ Application universal testing machine UTC-100 type (the オ リ エ of Co., Ltd. Application テ StarNetwork).Said determination is fixed on the roughly center of clamp spacing with the lap of sample, makes that spacing jig is 50mm, draw speed is the 300mm/ branch, implements tension test under 23 ℃ atmosphere, and the stress before lap has just been peeled off is measured.Tensile strength at diaphragm is lower, under in addition the situation of part fracture, 2 all overlapping 2 times diaphragms is used as one group, according to measuring with above-mentioned the same method before lap is peeled off.Each benchmark is measured 5 times during mensuration, and the mean value of obtaining 5 tests is as cohesive force.
The polylactic acid base polymer that uses in the present embodiment, fluidizer obtains in such a way.
(polylactic acid base polymer (P1))
The stannous octoate that mixes 0.02 weight part with respect to 100 weight part L-lactides, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 15 minutes, after further carrying out sheet with the twin shaft mixing extruder, in 140 ℃ nitrogen atmosphere, carry out 3 hours solid state polymerization, obtain polylactic acid base polymer P1.When P1 was carried out DSC mensuration, P1 had crystallinity, and crystallized temperature is 128 ℃, and fusing point is 172 ℃.
(polylactic acid base polymer (P2))
The stannous octoate that mixes 0.02 weight part with respect to the L-lactide and the 35 weight part DL-lactides of 65 weight parts, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere,, further carry out sheet, obtain polylactic acid base polymer P2 with the twin shaft mixing extruder with 190 ℃ of following polymerizations 40 minutes.When P2 was carried out DSC mensuration, P2 did not show crystallinity, does not observe crystallized temperature and fusing point.
(polylactic acid base polymer (P3))
The stannous octoate that mixes 0.02 weight part with respect to the L-lactide and the 14 weight part DL-lactides of 86 weight parts, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere,, further carry out sheet, obtain polylactic acid base polymer P3 with the twin shaft mixing extruder with 190 ℃ of following polymerizations 40 minutes.When P3 was carried out DSC mensuration, P3 had crystallinity, and fusing point is 141 ℃.
(fluidizer (S1))
It with respect to 40 weight part molecular-weight average 8000 poly-(hexanodioic acid 1, the 3-butanediol ester) and the L-lactide of 60 weight parts mix the stannous octoate of 0.025 weight part, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, acquisition has the segmented copolymer S1 that molecular-weight average is 6000 poly(lactic acid) segmental poly-(hexanodioic acid 1,3 butylene glycol ester) and poly(lactic acid) two ends.The Δ H of S1 P0Be 23.3J/g, Δ H P0Peak temperature be 145.0 ℃.
(fluidizer (S2))
It with respect to 71 weight part molecular-weight average 10000 poly-(hexanodioic acid 1, the 3-butanediol ester) and the L-lactide of 29 weight parts mix the stannous octoate of 0.025 weight part, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, acquisition has the segmented copolymer S2 that molecular-weight average is 2000 poly(lactic acid) segmental poly-(hexanodioic acid 1,3 butylene glycol ester) and poly(lactic acid) two ends.The Δ H of S2 P0Be 11.4J/g, Δ H P0Peak temperature be 124.1 ℃.
(fluidizer (S3))
Be that the additional ring oxidative ethane is made on two ends of 2000 polypropylene glycol molecular weight is the stannous octoate that the L-lactide of 10000 polypropylene glycol-ethylene glycol segmented copolymer and 29 weight parts mixes 0.025 weight part with respect to 71 weight parts at molecular-weight average, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, obtain to have molecular-weight average and be 2000 the segmental polypropylene glycol-ethylene glycol of poly(lactic acid) and the segmented copolymer S3 of poly(lactic acid) two ends.The Δ H of S3 P0Be 15.8J/g, Δ H P0Peak temperature be 131.8 ℃.
(fluidizer (S4))
With respect to 71 weight part molecular-weight average is the stannous octoate that the L-lactide of 10000 polyoxyethylene glycol and 29 weight parts mixes 0.025 weight part, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, obtain to have molecular-weight average and be 2000 the segmental polyoxyethylene glycol of poly(lactic acid) and the segmented copolymer S4 of poly(lactic acid) two ends.The Δ H of S4 P0Be 17.0J/g, Δ H P0Peak temperature be 135.0 ℃.
(fluidizer (S5))
The ether-ether class fluidizer " RS-1000 " (being liquid under the room temperature) that Xu Dianhuagongyeshe is made uses as fluidizer S5.
(fluidizer (S6))
Be that 8000 polyoxyethylene glycol uses as fluidizer S6 with molecular-weight average.
(fluidizer (S7))
With respect to 80 weight part molecular-weight average is the stannous octoate that the L-lactide of 8000 polyoxyethylene glycol and 20 weight parts mixes 0.025 weight part, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, obtain to have molecular-weight average and be 1000 the segmental polyoxyethylene glycol of poly(lactic acid) and the segmented copolymer S7 of poly(lactic acid) two ends.S7 does not observe Δ H P0
(fluidizer (S8))
With respect to 79 weight part molecular-weight average is the stannous octoate that the L-lactide of 10000 polyoxyethylene glycol and 21 weight parts mixes 0.025 weight part, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, obtain to have molecular-weight average and be 1300 the segmental polyoxyethylene glycol of poly(lactic acid) and the segmented copolymer S8 of poly(lactic acid) two ends.The Δ H of S8 P0Be 9.2J/g, Δ H P0Peak temperature be 122.0 ℃
Measure the chart of the heavy chloroformic solution gained of fluidizer (S8) based on 1H-NMR, according to
(1/2)×(I PLA×72)/(I PEG×44/4)×M PEG
(wherein, I PEGBe the signal integration intensity from the hydrogen of the methylene radical of PEG main chain portion, I PLABe the signal integration intensity from the hydrogen of the methylene radical of PLA main chain portion, M PEGMolecular-weight average for polyoxyethylene glycol)
The segmental number-average molecular weight of the poly(lactic acid) that formula is calculated is 1260.
This value with from adding raw material ratio, according to
(1/2)×(W A/W B)×M PEG
(wherein, W A: L-lactide weight part, W B: polyoxyethylene glycol weight part, M PEGMolecular-weight average for polyoxyethylene glycol)
The value that formula is calculated is very well corresponding.
(fluidizer (S9))
With respect to 71 weight part molecular-weight average is the stannous octoate that the L-lactide of 10000 poly glycol monomethyl ether and 29 weight parts mixes 0.025 weight part, in the reaction vessel of whipping appts is installed, in nitrogen atmosphere and 190 ℃ of following polymerizations 60 minutes, obtain to have molecular-weight average and be 4000 the segmental poly glycol monomethyl ether of poly(lactic acid) and the segmented copolymer S9 of poly(lactic acid) in single end.The Δ H of S9 P0Be 21.8J/g, Δ H P0Peak temperature be 134.8 ℃.
(inorganic particle (F1))
Commercially available calcium carbonate powders is used as inorganic particle F1.
(embodiment 1)
With the mixture of 50 weight part polylactic acid base polymers (P1) and 50 weight part fluidizers (S1) at 100 ℃ of following drying under reduced pressure after 6 hours, offer bowl temperature and be 200 ℃ twin shaft mixing extruder, after homogenizing by melting mixing, make the shred composition.The composition of gained is transparent.
Adopting said composition, is 200 ℃ with the cylinder temperature, die temperature be 20 ℃ emission forming machine to be configured as width be 12mm, thickness is the modulus in flexure test film of 6mm.In addition, the composition that adopts same way as to obtain by 190 ℃ hot pressing, is configured as thickness and is 200 microns compressing tablet, and the evaluation result of test film and compressing tablet is shown in table 1.
(embodiment 2)
Except the mixture that adopts 72 weight part polylactic acid base polymers (P1) and 28 weight part fluidizers (S2), implement according to the mode the same with embodiment 1, obtain the shred composition.The composition of gained is transparent.
Adopt said composition, under the condition the same, be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 3)
Except the mixture that adopts 51 weight part polylactic acid base polymers (P1) and 49 weight part fluidizers (S2), implement according to the mode the same with embodiment 1, obtain the shred composition.The composition of gained has some oyster whites, and is simultaneously almost transparent.
Adopt said composition, under the condition the same, be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 4)
Except Hinered phenols oxidation inhibitor " the イ Le ガ ノ that adopts 72 weight part polylactic acid base polymers (P1) and 28 weight part fluidizers (S3) and 0.3 weight part チ バ ガ イ ギ, one society to make StarNetwork ス 1010 " mixture beyond, implement according to the mode the same with embodiment 1, obtain the shred composition.The composition of gained is transparent.
Adopt said composition, under the condition the same, be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 5)
Except Hinered phenols oxidation inhibitor " the イ Le ガ ノ that adopts 94 weight part polylactic acid base polymers (P1) and 6 weight part fluidizers (S3) and 0.3 weight part チ バ ガ イ ギ, one society to make StarNetwork ス 1010 " mixture beyond, implement according to the mode the same with embodiment 1, obtain the shred composition.The composition of gained is transparent.
Adopt said composition, under the condition the same, be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 6)
Except Hinered phenols oxidation inhibitor " the イ Le ガ ノ that adopts 72 weight part polylactic acid base polymers (P1) and 28 weight part fluidizers (S4) and 0.3 weight part チ バ ガ イ ギ, one society to make StarNetwork ス 1010 " mixture beyond, implement according to the mode the same with embodiment 1, obtain the shred composition.The composition of gained is transparent.
Adopt said composition, under the condition the same, be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 7)
The compressing tablet that employing obtains according to the mode the same with embodiment 6, draft temperature at 70 ℃, and make the stretching ratio on the vertical and horizontal be 3.2 times simultaneously, the area multiplying power be 10 times ground modes carry out the while biaxial stretch-formed after, heat treated is 20 seconds in 140 ℃ atmosphere, is configured as biaxially oriented film.The biaxially oriented film of gained is transparent.Evaluation result to biaxially oriented film is shown in table 1.
(embodiment 8)
Except Hinered phenols oxidation inhibitor " the イ Le ガ ノ that adopts 75 weight part polylactic acid base polymers (P1) and 25 weight part fluidizers (S8) and 0.3 weight part チ バ ガ イ ギ, one society to make StarNetwork ス 1010 " mixture beyond, implement according to the mode the same with embodiment 1, obtain the shred composition.The composition of gained is transparent.
Adopt said composition, adopt the mode the same to be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 9)
Adopt 37 weight parts decompressions down and the polylactic acid base polymer (P1) of 6 hours gained of 100 ℃ of following drying under reduced pressure and the decompression of 35 weight parts down and 50 ℃ of following drying under reduced pressure 48 hours or the polylactic acid base polymer (P2) of its above gained and Hinered phenols oxidation inhibitor " the イ Le ガ ノ of 0.3 weight part チ バ ガ イ ギ, one society manufacturing StarNetwork ス 1010 " mixture, it is provided to the cylinder temperature is 200 ℃ twin shaft mixing extruder, and carries out melting mixing, after homogenizing, obtains the shred composition.The composition of gained is transparent.
Adopt said composition, adopt the mode the same to be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1 by 190 ℃ hot pressing.
(embodiment 10)
Except adopt 45 weight parts decompressions down and the polylactic acid base polymer (P1) of 6 hours gained of 100 ℃ of following drying under reduced pressure, 20 weight part fluidizers (S6), the decompression of 35 weight parts down and 50 ℃ of following drying under reduced pressure 48 hours or the polylactic acid base polymer (P2) of its above gained and Hinered phenols oxidation inhibitor " the イ Le ガ ノ of 0.3 weight part チ バ ガ イ ギ, one society manufacturing StarNetwork ス 1010 " mixture beyond, make the shred composition according to the mode the same with embodiment 9.The composition of gained is transparent.
Adopt said composition, adopt the mode the same to be configured as the modulus in flexure test film with embodiment 1.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 2 by 190 ℃ hot pressing.
(embodiment 11)
Except adopting Hinered phenols oxidation inhibitor " the イ Le ガ ノ of polylactic acid base polymer (P3), 20 weight part fluidizers (S6) and the manufacturing of 0.3 weight part チ バ ガ イ ギ, one society of crossing with 80 ℃ of following drying under reduced pressure under the decompression of 80 weight parts StarNetwork ス 1010 " mixture beyond, make the shred composition according to the mode the same with embodiment 9.The composition of gained is transparent.
Adopt said composition, adopt the mode the same to be configured as the modulus in flexure test film with embodiment 1.In addition, adopting identical composition, is that thickness is 200 microns compressing tablet by 190 ℃ hot compactings, and the evaluation result of test film and compressing tablet is shown in table 3.
(embodiment 12)
Except adopting fluidizer (S9) to replace the fluidizer (S4), make composition according to the mode the same with embodiment 6.The composition of gained is transparent.Adopt said composition, be configured as the modulus in flexure test film according to the mode the same with embodiment 1.In addition, adopting identical composition, is that thickness is 200 microns compressing tablet by 190 ℃ hot compactings, and the evaluation result of test film and compressing tablet is shown in table 1.
(embodiment 13)
Except adopt 72 weight parts decompressions down and 50 ℃ of following drying under reduced pressure 48 hours or the polylactic acid base polymer (P2) more than it, the decompression of 28 weight parts down and Hinered phenols oxidation inhibitor " the イ Le ガ ノ that makes of 100 ℃ of fluidizers of 6 hours of following drying under reduced pressure (S4) and 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture beyond, make the shred composition according to the mode the same with embodiment 9.The composition of gained is transparent.
Adopt said composition, be configured as the modulus in flexure test film according to the mode the same with embodiment 1.In addition, adopting identical composition, is that thickness is 200 microns compressing tablet by 190 ℃ hot compactings, and the evaluation result of test film and compressing tablet is shown in table 4.
(comparative example 1)
Except adopting polylactic acid base polymer (P1) and do not add the fluidizer, be configured as the modulus in flexure test film according to the mode the same with embodiment 1.In addition, adopting identical composition, is that thickness is 200 microns compressing tablet by 190 ℃ hot compactings, and the evaluation result of test film and compressing tablet is shown in table 1, table 2, table 3 and the table 4.
(comparative example 2)
Adopt 80 weight parts decompressions down and the mixture of the commercially available ether-ether class fluidizer (S5) of 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure (P1) and 20 weight parts, it is provided to the cylinder temperature is 200 ℃ twin shaft mixing extruder, and carry out melting mixing, after homogenizing, obtain the shred composition.The composition of gained is transparent.
Adopting said composition, is that 200 ℃, die temperature are that to be configured as width in 20 ℃ the emission forming machine be 12mm in the cylinder temperature, and thickness is the modulus in flexure test film of 6mm.In addition, adopt identical composition,, be configured as thickness and be 200 microns compressing tablet, the evaluation result of test film and compressing tablet is shown in table 1, table 2, table 3 and the table 4 by 190 ℃ hot pressing.
(comparative example 3)
Except adopt 80 weight parts decompressions down and 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure (P1), 20 weight parts do not have molecular weight 1200 or Hinered phenols oxidation inhibitor " the イ Le ガ ノ that makes of the segmental fluidizer of poly(lactic acid) (S6) more than it and 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture beyond, make the shred composition according to the mode the same with comparative example 2.Do not add and do not have crystalline polylactic acid base polymer (P2) or have crystal type, but the polylactic acid base polymer (P3) of 145 ℃ of fusing point less thaies.The composition of gained is transparent.
Adopt said composition, be configured as the modulus in flexure test film according to the mode the same with embodiment 1.In addition, adopting identical composition, is that thickness is 200 microns compressing tablet by 190 ℃ hot compactings, and the evaluation result of test film and compressing tablet is shown in table 1, table 2, table 3 and table 4.
(comparative example 4)
Except adopt 75 weight parts decompressions down and 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure (P1), 25 weight parts do not have molecular weight 1200 or Hinered phenols oxidation inhibitor " the イ Le ガ ノ that makes of the segmental fluidizer of poly(lactic acid) (S7) more than it and 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture beyond, make the shred composition according to the mode the same with comparative example 2.Do not add and do not have crystalline polylactic acid base polymer (P2) or have crystallinity, but the polylactic acid base polymer (P3) of 145 ℃ of fusing point less thaies.The composition of gained is transparent.
Adopt said composition, be configured as the modulus in flexure test film according to the mode the same with embodiment 1.In addition, adopting identical composition, is that thickness is 200 microns compressing tablet by 190 ℃ hot compactings, and the evaluation result of test film and compressing tablet is shown in table 1, table 2, table 3 and table 4.
(comparative example 5)
The compressing tablet that adopts the mode the same to make with comparative example 4, at 70 ℃ draft temperature, and make the stretching ratio on the vertical and horizontal be 3.2 times simultaneously, the area multiplying power be 10 times ground modes carry out the while biaxial stretch-formed after, heat treated is 20 seconds in 140 ℃ atmosphere, forms biaxially oriented film.The biaxially oriented film of gained is transparent.Evaluation result to biaxially oriented film is shown in table 1, table 2, table 3 and table 4.
Figure A20081009125300331
Figure A20081009125300341
Figure A20081009125300351
(embodiment 14)
Adopt under the decompression of 57 weight parts and the mixture of 100 ℃ of 6 hours polylactic acid base polymers of following drying under reduced pressure (P1) and 43 weight part fluidizers (S2), it is provided to the cylinder temperature is 200 ℃ twin shaft mixing extruder, and carry out melting mixing, after homogenizing, obtain the shred composition.Resulting composition is transparent.Said composition (flap) under reduced pressure with 80 ℃ of following dryings 24 hours or more than it, is provided in the following system film.
Above-mentioned flap is set at 210 ℃ single shaft forcing machine fusion with melt temperature, the fused polymkeric substance is imported in the T mould die orifice, be extruded into sheet, pour into a mould being cooled on 5 ℃ the drum, form non-stretched film.Stretch in the vertical between 60 ℃ warming mill 3.5 times continuously, the stretching device that after this adopts the tenter machine mode after 3.0 times of stretching setting multiplying powers on the width, 130 ℃ of thermal treatments, is reeled to film under Stress under 65 ℃.The thickness of gained film is 12 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 15)
Except the mixture that uses 72 weight part polylactic acid base polymers (P1) and 28 weight part fluidizers (S3), obtain biaxially oriented film according to the mode the same with embodiment 14.The thickness of gained film is 15 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 16)
Except using 86 weight part polylactic acid base polymers (P1) and 14 weight part fluidizers (S4), and Hinered phenols oxidation inhibitor " the イ Le ガ ノ that makes of 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 14.The thickness of gained film is 40 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 17)
Except using 72 weight part polylactic acid base polymers (P1) and 28 weight part fluidizers (S4), and Hinered phenols oxidation inhibitor " the イ Le ガ ノ that makes of 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 14.The thickness of gained film is 18 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 18)
Except using 70 weight part polylactic acid base polymers (P1), 28 weight part fluidizers (S4), Hinered phenols oxidation inhibitor " the イ Le ガ ノ that 2 weight part inorganic particles (F1) and 0.3 weight part チ バ ガ イ ギ, one society make StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 14.The thickness of gained film is 38 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 19)
Adopt 17 weight parts decompressions down and 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure (P1) and 28 weight part fluidizers (S4), the decompression of 55 weight parts down and Hinered phenols oxidation inhibitor " the イ Le ガ ノ of 50 ℃ of following drying under reduced pressure 48 hours or its above polylactic acid base polymer (P2) and the manufacturing of 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture, it is provided to the cylinder temperature is 200 ℃ twin shaft mixing extruder, and carries out melting mixing, after homogenizing, obtains the shred composition.Said composition (flap) under reduced pressure with 70 ℃ of following dryings 24 hours or more than it, is provided in the following system film.
Above-mentioned shred thing is set at 210 ℃ single shaft forcing machine fusion with melt temperature, the fused polymkeric substance is imported in the circular mode, be extruded into shred, adopt about 5 ℃ cold water to cool off fast, after this, it is biaxial stretch-formed to adopt blowing process to carry out while under 55 ℃ heating, makes to be drawn into 4 times on vertical, is drawn into 4 times on the width.After this by being set in the thermal treatment zone under the preset temperature, the film of gained is reeled.The thickness of gained film is 12 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 20)
Except using 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure of 27 weight parts (P1), 43 weight part fluidizers (S4), Hinered phenols oxidation inhibitor " the イ Le ガ ノ that 50 ℃ of following drying under reduced pressure of 30 weight parts 48 hours or its above polylactic acid base polymer (P2) and 0.3 weight part チ バ ガ イ ギ, one society make StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 19.The thickness of gained film is 12 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 21)
Except Hinered phenols oxidation inhibitor " the イ Le ガ ノ that uses 75 weight part polylactic acid base polymers (P1) and 0.3 weight part チ バ ガ イ ギ, one society to make StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 14.The thickness of gained film is 18 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 22)
Except using 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure of 37 weight parts (P1), 28 weight part fluidizers (S4), and Hinered phenols oxidation inhibitor " the イ Le ガ ノ that makes of 50 ℃ of following drying under reduced pressure of 35 weight parts 48 hours or its above polylactic acid base polymer (P2) and 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 19.The thickness of gained film is 18 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5.
(embodiment 23)
Except using 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure of 45 weight parts (P1), 20 weight part fluidizers (S6), Hinered phenols oxidation inhibitor " the イ Le ガ ノ that 50 ℃ of following drying under reduced pressure of 35 weight parts 48 hours or its above polylactic acid base polymer (P2) and 0.3 weight part チ バ ガ イ ギ, one society make StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 19.The thickness of gained film is 15 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 6.
(embodiment 24)
Except Hinered phenols oxidation inhibitor " the イ Le ガ ノ that uses 80 ℃ of polylactic acid base polymers of 12 hours of following drying under reduced pressure of 80 weight parts (P3), 20 weight part fluidizers (S6) and 0.3 weight part チ バ ガ イ ギ, one society to make StarNetwork ス 1010 " mixture beyond, obtain biaxially oriented film according to the mode the same with embodiment 19.The thickness of gained film is 15 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 7.
(embodiment 25)
The compressing tablet that adopts the mode the same with embodiment 13 to make at 55 ℃ draft temperature, and makes the stretching ratio on the vertical and horizontal be 3.2 times simultaneously, the area multiplying power be 10 times modes to carry out the while biaxial stretch-formed, the formation biaxially oriented film.
The evaluation result of the biaxially oriented film of gained is shown in table 8.
(comparative example 6)
Only used 100 ℃ of following drying under reduced pressure 12 hours or the polylactic acid base polymer (P1) more than it, do not use fluidizer, be set at 210 ℃ single shaft forcing machine fusion with melt temperature, molten polymer is imported in the T mould die orifice that slit width is 1.0mm, be extruded into sheet, pour into a mould being cooled on about 15 ℃ drum, form non-stretched film.Stretch in the vertical between 85 ℃ warming mill 3.5 times continuously, the stretching device that after this adopts the tenter machine mode after 3.5 times of stretching setting multiplying powers on the width, 140 ℃ of thermal treatments, is reeled to the gained film under Stress under 80 ℃.The thickness of gained film is 20 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5, table 6, table 7 and the table 8.
(comparative example 7)
Use biaxial extruder in 200 ℃ of following fusions 100 ℃ of following drying under reduced pressure 12 hours or the polylactic acid base polymer (P1) more than it, the ratio that 25 weight parts (S5) are provided with per 75 weight parts (P1) is to commercially available ether-ether class fluidizer (S5) wherein is provided continuously, by fusion, mixing and homogenize after, obtain the shred composition.This fragment under reduced pressure with 80 ℃ of following dryings 24 hours or more than it, is provided in the following system film.
Above-mentioned fragment is set at 210 ℃ single shaft forcing machine fusion with melt temperature, the fused polymkeric substance is imported in the circular mode, be extruded into tubulose, adopt about 5 ℃ cold water to cool off fast, after this, it is biaxial stretch-formed to adopt blowing process to carry out while under 60 ℃ heating, makes to be drawn into 4 times on vertical, is drawn into 4 times on the width.After this by being set in the thermal treatment zone under the preset temperature, the film of gained is reeled.The thickness of gained film is 12 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5, table 6, table 7 and the table 8.
(comparative example 8)
Hinered phenols oxidation inhibitor " イ Le ガ ノ with 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure of 75 weight parts (P1), 25 weight part fluidizers (S6) and the manufacturing of 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture provide and be 200 ℃ twin shaft mixing extruder to the cylinder temperature, by fusion, mixing and homogenize after, obtain the shred composition.Do not add and do not have crystalline polylactic acid base polymer (P2) or have crystallinity, but the polylactic acid base polymer (P3) of 145 ℃ of fusing point less thaies.This fragment under reduced pressure with 80 ℃ of following dryings 24 hours or after more than it, is made biaxial stretch-formed film according to comparative example 7 the same methods, and the thickness of gained film is 12 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5, table 6, table 7 and the table 8.
(comparative example 9)
Hinered phenols oxidation inhibitor " イ Le ガ ノ with 100 ℃ of polylactic acid base polymers of 6 hours of following drying under reduced pressure of 67 weight parts (P1), 33 weight part fluidizers (S7) and the manufacturing of 0.3 weight part チ バ ガ イ ギ, one society StarNetwork ス 1010 " mixture provide and be 200 ℃ twin shaft mixing extruder to the cylinder temperature, by fusion, mixing and homogenize after, obtain the shred composition.Do not add and do not have crystalline polylactic acid base polymer (P2) or have crystallinity, but the polylactic acid base polymer (P3) of 145 ℃ of fusing point less thaies.This flap under reduced pressure with 80 ℃ of following dryings 24 hours or after more than it, is made biaxial stretch-formed film according to comparative example 7 the same methods, and the thickness of gained film is 12 microns.
The evaluation result of the biaxially oriented film of gained is shown in table 5, table 6, table 7 and the table 8.
(embodiment 26)
The Potato salad of packing in the bowl of glass, the film that adopts embodiment 19 cover the peristome of bowl as packaging film.Packaging film is along the fabulous sealing of the curved surface of the peristome of bowl, even also can keep sealed state after letting go, with being covered with of the peristome complete closed of bowl, operability is good.
Under this state, in refrigerator, after 1 week of keeping, keep sealed state equally.Do not find on the packaging film surface, to produce phenomenons such as adhesion.
Further cover and be contained in after meal cold in the teacup with above-mentioned film, when the state of observing after carrying out heat treated by microwave oven, find that film is damaged, not fusion of the film on the teacup, no change before the transparency of film and the heat treated, and the phenomenon that on film surface, also is not clamminess.
(embodiment 27)
The overlapping placement of each section 4 bags of the paper bags of 25kg poly(lactic acid) fragment of having packed into amount to 5 sections on ligneous pad, and the film of embodiment 22 is used as the pad stretch wrappers, be wound on the eclipsed paper bag around.The stretchiness of film is enough, and along the extraordinary distortion of eclipsed paper bag.And do not scatter under state of nature in the back of reeling, cohesiveness is enough yet, and operability is good.
(embodiment 28)
Except thickness being changed to 25 microns, obtain film according to embodiment 18 the same modes.Be laid on the farmland in the Shiga Prefecture according to the mode the same with commercially available agricultural multi-usage film.This film has the flexibility of appropriateness, and the part of the soil come-up of having no way of can be easy to lay along the soil shape.In addition, when laying operation, even trample film, film is not damaged yet, and does not produce fold.
In addition, have flexibility almost equal when laying placing above-mentioned film after 3 months, the phenomenon of breakage or surface adhesion do not occur.In addition, after placing 9 months, a part of breakage or one-tenth part shape at random take place owing to decompose acceleration in film.When by the employing cultivator each film being carried out hoe, film is pulverized easily, and can uproot in the soil.
(embodiment 29)
The film that adopts embodiment 18 is as the base material film, coating is dissolved in the solution that forms in 94 parts by weight of toluene with 5 weight part natural rubbers, 1 weight part natural rosin on film surface, drying, formation thickness is 15 microns tack coat, is made into adhesive label.The lip-deep paper label of empty Beer Bottle is fully removed, cleaned, after the drying, labels on the Beer Bottle surface and pay when above-mentioned, and label itself is along Beer Bottle curved surface tight bond.Further the part of label is pasted when paying on the shoulder of Beer Bottle to articulate mode, owing to have the extensibility of appropriateness, so label itself is along Beer Bottle curved surface tight bond.
(embodiment 30)
The film that adopts embodiment 16 is as the base material film, coating is dissolved in the solution that forms in 94 parts by weight of toluene with 5 weight part natural rubbers, 1 weight part natural rosin on film surface, dry, formation thickness is 15 microns tack coat, crimping makes adhesive tape by the stripping film that polyvinyl alcohol (PVA) film forms on tie layer surface.When this band being carried out the bale packing operation, it has enough extensibilities along closely being followed by the curved surface of package, the operability excellence.
(embodiment 31)
Adopt the raw material of forming similarly to Example 18, adopt blowing extrusion molding method, be configured as thickness and be 20 microns film, it is cut and refuse bag is made in heat-sealing.This refuse bag is replaced commercially available polyethylene system refuse bag, and when being used for the domestic refuse discharging, perforate does not take place in flexibility and disguise that it has appropriateness, and breakage does not take place curved part yet, and operability is good.
(embodiment 32)
Except the thermal treatment temp after will stretching is set at 60 ℃, the thickness of film is changed into beyond 18 microns, make film according to the mode the same with embodiment 16.Adopt this film,, packing by biaxial stretch-formed polystyrene system and covering material and added the commercially available disposable packed meal container that steatitic PP system ground forms 3 limit heat seals of film.This packed meal container is that 100 ℃ hot air type baking oven system is when carrying out about 1 minute thermal treatment at storehouse temperature, make the warpage of film by thermal contraction along with the packed meal container, do not produce the relaxation phenomenon that film contraction non-uniform phenomenon and film float from vessel surface, with the whole extraordinary packings of container.In addition, film is not damaged yet, and film is not melted on the container yet.Compare no change before the transparency of film and the thermal treatment, and on film surface, adhesion phenomenon does not take place.
Utilizability on the industry
Polylactic acid base polymer composition of the present invention is not mention in the prior art, has enough flexibilities, few fluidizer that produces volatilize, oozes out, runs off (bleed-out) and bleach when heating and the polylactic acid base polymer composition of problem such as muddiness when using as molding.Polylactic acid base polymer composition of the present invention particularly as the molding such as film of packaging packaging film etc., can extensively utilize.
In addition, polylactic acid base polymer composition of the present invention is compared with existing plastics, and its advantage is the biological degradability height in physical environment, uses the back to decompose than being easier in physical environment.Polylactic acid base polymer composition of the present invention is extremely useful to the environmental problem that the solution plastic refuse causes.
Figure A20081009125300431
Figure A20081009125300451
Figure A20081009125300461

Claims (12)

1. the tensile modulus that the polylactic acid base polymer composition shaping is obtained is 100～1500MPa, and cohesive force is 5～30N/cm 2Film, described polylactic acid base polymer composition comprises and has crystalline polylactic acid base polymer and fluidizer, it is characterized by, fluidizer is that to have one or more molecular weight in 1 molecule be 1200 or the poly(lactic acid) fragment more than it, and has the segmental fluidizer of polyester.
2. the tensile modulus that the polylactic acid base polymer composition shaping is obtained is 100～1500MPa, and cohesive force is 5～30N/cm 2Film, described polylactic acid base polymer composition comprises and has crystalline polylactic acid base polymer, do not have crystalline polylactic acid base polymer and fluidizer, it is characterized by, fluidizer is to have the polyester fragment, and not have molecular weight be 1200 or its above segmental fluidizer of poly(lactic acid).
3. the tensile modulus that the polylactic acid base polymer composition shaping is obtained is 100～1500MPa, and cohesive force is 5～30N/cm 2Film, described polylactic acid base polymer composition comprise have crystallinity, the polylactic acid base polymer and the fluidizer of 145 ℃ of fusing point less thaies, it is characterized by, fluidizer is to have the polyester fragment, and not have molecular weight be 1200 or its above segmental fluidizer of poly(lactic acid).
4. film as claimed in claim 1 is characterized by and has the segmental fluidizer of polyester to have one or more molecular weight in its 1 molecule be 1500 or the poly(lactic acid) fragment more than it.
5. as claim 1 or 3 described films, it is characterized by polylactic acid base polymer composition and contain and do not have crystalline polylactic acid base polymer.
6. as claim 1,2 or 3 described films, it is characterized by the 50 whole weight % of the not enough fluidizer of the segmental part by weight of poly(lactic acid) of fluidizer.
7. as claim 1,2 or 3 described films, the part by weight that it is characterized by the plasticization composition except the poly(lactic acid) fragment of fluidizer is 5 all weight % of composition～30 weight %.
8. as claim 1,2 or 3 described films, it is characterized by is with polylactic acid base polymer composition stretch on the single shaft direction at least 1.1 times or the film that forms more than it.
9. as claim 1,2 or 3 described films, thermotolerance is 120-230 ℃.
10. as claim 1,2 or 3 described films, its film turbidity value is 0.2-5%.
11. as claim 1,2 or 3 described films, be applied to packaging packaging film, stretch wrappers, agricultural film, label with film, adhesive tape with film, base material protection with film or bag with in film any.
12. the tensile modulus that the polylactic acid base polymer composition shaping is obtained is 100～1500MPa, cohesive force is 5～30N/cm 2Film, the combination of described polylactic acid base polymer comprises and does not have crystalline polylactic acid base polymer and fluidizer, does not have crystalline polylactic acid base polymer and do not contain, it is characterized by fluidizer is to have the segmental fluidizer of polyester.
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